Metallurgy of soft spheres with hard core: from BCC to Frank-Kasper phases

TL;DR

This paper investigates how the interplay between van der Waals attraction and elastic deformation influences the formation of complex nanoparticle superlattices, revealing conditions favoring BCC or Frank-Kasper phases.

Contribution

It introduces a model comparing van der Waals forces and elastic energy to predict structural preferences in soft sphere systems with hard cores.

Findings

Elastic energy favors BCC structures

Van der Waals forces promote Frank-Kasper phases

Model suggests control over nanoparticle superlattice formation

Abstract

Understanding how soft particles can fill the space is still an open question. Structures far from classical FCC or BCC phases are now commonly experimentally observed in many different systems. Models based on pair interaction between soft particle are at present much studied in 2D. Pair interaction with two different lengths have been shown to lead to quasicrystalline architectures. It is also the case for a hard core with a square repulsive shoulder potential. In 3D, global approaches have been proposed for instance by minimizing the interface area between the deformed objects in the case of foams or micellar systems or using self-consistent mean field theory in copolymer melts. In this paper we propose to compare a strong van der Waals attraction between spherical hard cores and an elastic energy associated to the deformation of the soft corona. This deformation is measured as the shift between the deformed shell compared to a corona with a perfect spherical symmetry. The two main parameters in this model are: the hard core volume fraction and the weight of the elastic energy compared to the van der Waals one. The elastic energy clearly favours the BCC structure but large van der Waals forces favors Frank and Kasper phases. This result opens a route towards controlling the building of nanoparticle superlattices with complex structures and thus original physical properties.